KR20040022427A - A thermoplastic resin composition - Google Patents

Abstract

A thermoplastic resin composition which has been highly effectively plasticized and has excellent flexibility. It comprises a polymer and a thermoplastic resin. The polymer comprises at least 20 wt.% units of at least one monomer represented by any of the following chemical formulae (1) to (4) and up to 80 wt.% other monomer units. The resin may be a polymethyl methacrylate resin, vinyl chloride resin, ABS resin, etc. CH2=CHCOO(CH2CH2O)m-R (1) CH2=C(CH3)COO(CH2CH2O)m-R (2) CH 2=CHCOO(CH2C(CH3)HO)m-R (3) CH2 =C(CH3)COO(CH2C(CH3)HO)m-R (4) In the chemical formulae (1) to (4), m is 1, 2, or 3 and R represents hydrogen or C1-4 alkyl.

Description

Thermoplastic composition {A THERMOPLASTIC RESIN COMPOSITION}

In general, when molding a composition in which a general plasticizer such as dioctylphthalate (DOP) is blended, there is a problem in that plasticity and flexibility of the molded product decrease over time or the surface of the molded product becomes sticky. In order to improve such a problem, the following improvement of the composition is disclosed.

Japanese Patent Laid-Open No. 55-160045 discloses a composition for improving the processability of vinyl chloride resin. The composition consists of two types of polymer components. The first polymer component is a mixture containing 0.1 to 10% by weight of (meth) acrylate, 20 to 99.9% by weight of other alkyl acrylate, and 79.9 to 0% by weight of vinyl monomer copolymerizable with them. It is obtained by performing a polymerization reaction. The (meth) acrylate has a glycidyl group, a hydroxyl group, or an alkoxy group. The second polymer component is obtained by subjecting the mixture to a mixture containing 50 to 100 wt% of methyl methacrylate and 0 to 50 wt% of other vinyl monomers copolymerizable therewith.

In addition, thermoplastic resin compositions obtained by blending specific copolymers with polycarbonate resins are also known (Patent No. 2000-178432). The specific copolymer is copolymerizable with 0.1 to 10% by weight of the first (meth) acrylic acid ester, 5 to 90% by weight of the second (meth) acrylic acid ester, 5 to 70% by weight of an aromatic vinyl compound, and those It is obtained by performing a copolymerization reaction with respect to the component which consists of other components 0-50 weight%. The said 1st (meth) acrylic acid ester has an epoxy group, a hydroxyl group, or an alkoxy group.

By the way, the composition used as the processability improvement agent of the vinyl chloride resin of the said document was not compatible with the same composition and vinyl chloride resin. In addition, the thermoplastic resin composition of the above document did not have sufficient compatibility with the polycarbonate resin and the specific copolymer added thereto. Therefore, since the plasticization effect falls and there is a flaw in flexibility, there is a problem in that its use is limited in use.

The present invention relates to a thermoplastic resin composition having good flexibility, and more particularly, to a resin such as polymethyl methacrylate resin, vinyl chloride resin, acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as ABS resin). It relates to the improvement of the composition consisting of.

The present invention has been made in view of the problems existing in the prior art as described above. The purpose is to provide a thermoplastic resin composition having high plasticizing effect and good flexibility.

In order to achieve the above object, the composition of the present invention or the processed article obtained from the composition consists of a specific polymer and a thermoplastic resin. In one embodiment, the polymer contains 20% by mass or more of the monomer units represented by any one of Formulas (1) to (4) shown below, and 80% by mass or less of other monomer units.

CH ₂ = CHCOO (CH ₂ CH ₂ O) m -R. (One)

CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) m R. (2)

CH ₂ = CHCOO (CH ₂ C (CH ₃ ) HO) m R. (3)

CH ₂ = C (CH ₃ ) COO (CH ₂ C (CH ₃ ) HO) m R. (4)

In the formulas (1) to (4), m is 1, 2, or 3. R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Except that m is 1 and R is a hydrogen atom.

In one embodiment of the present invention, the polymer described above has a low weight average molecular weight of 500 to 10,000.

The composition of this invention is based on 100 mass parts of thermoplastic resins in one embodiment, and contains the said polymer in content of 10-200 mass parts.

In one embodiment of the composition of the present invention, the thermoplastic resin is a polymethylmethacrylate resin. In another embodiment, the thermoplastic resin is vinyl chloride resin. In yet another embodiment, the thermoplastic resin is an acrylonitrile-butadiene-styrene copolymer. In yet another embodiment, the thermoplastic resin is AXS resin. Here, AXS resin is a copolymer resin of acrylonitrile, rubber components other than butadiene, and styrene.

The thermoplastic resin composition preferably has an elongation rate of the thermoplastic resin composition that is at least 30% greater than the elongation rate of the thermoplastic resin, more preferably 50% or more, and most preferably 70% or more. The thermoplastic resin composition is preferably 30% or more larger than the elongation of the composition in which only the polymer is removed among the components included in the thermoplastic resin composition (hereinafter, referred to as a composition not containing a polymer). More preferably 50% or more, and most preferably 70% or more. Here, "30%", "50%" and "70%" are not an increase rate of elongation based on the elongation rate of the composition which does not include the thermoplastic resin or the polymer, but include the thermoplastic resin or the polymer at the elongation rate of the thermoplastic resin composition. It means the absolute value of the increase in elongation minus the elongation of the composition is not.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The thermoplastic resin composition consists of a specific polymer and a thermoplastic resin. The polymer consists of a first monomer unit and a second monomer unit different from that. In other words, the first monomer unit and the second monomer unit are units constituting the polymer. The first monomer unit is represented by any one of the formulas (1) to (4) shown below, and is contained in the polymer at 20 mass% or less. The second monomer unit is included at 80 mass% or less in the polymer.

CH ₂ = CHCOO (CH ₂ CH ₂ O) m -R. (One)

CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) m R. (2)

CH ₂ = CHCOO (CH ₂ C (CH ₃ ) HO) m R. (3)

CH ₂ = C (CH ₃ ) COO (CH ₂ C (CH ₃ ) HO) m R. (4)

Here, in the formulas (1) to (4), m is 1, 2, or 3. R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Except that m is 1 and R is a hydrogen atom.

In the formulas (1) to (4), R is preferably an alkyl group having 1 to 4 carbon atoms. In this case, the compatibility between the polymer and the resin is improved, the plasticizing effect is high, and the flexibility can be improved.

A polymer is obtained by superposing | polymerizing the (meth) acrylic-acid alkoxy alkyl which is a monomer of general formula (1)-(4), and another monomer. Below, the monomer used as a raw material of a polymer is illustrated and described in detail. As a monomer of General formula (1), it may be methoxy ethyl acrylate, ethoxy ethyl acrylate, butoxy butyl ethyl. As a monomer of General formula (2), it may be methoxy ethyl methacrylate, ethoxy ethyl methacrylate, butoxy ethyl methacrylate. As the monomer of the general formula (3), it may be methoxy isopropyl acrylate, ethoxy isopropyl acrylate, butoxy propyl isopropyl acrylate. As the monomer of the formula (4), it may be methoxy isopropyl methacrylate, ethoxy methacrylate isopropyl, methacrylic acid butoxy propyl propyl. Particularly preferred monomers are methoxyethyl (meth) acrylate or ethoxyethyl (meth) acrylate, and the most preferred monomer is methoxyethyl acrylate. The other monomer polymerized with the (meth) acrylate alkoxyalkyl is preferably a monomer copolymerizable with the monomers represented by the formulas (1) to (4). For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, (meth) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, styrene and the like. In this specification, (meth) acrylic is a generic term for acryl and methacryl.

The said polymer contains 20 mass% or more of a 1st monomeric unit and 80 mass% or less of a 2nd monomeric unit. If the first monomer unit is less than 20% by mass, that is, if the second monomer unit exceeds 80% by mass, a composition having high plasticizing effect and excellent flexibility cannot be obtained.

It is preferable that the said polymer is a low molecular weight of 500-10000 in weight average molecular weight. When the weight average molecular weight of a polymer exceeds 10000, there exists a tendency for the plasticization effect to fall by a polymer. On the other hand, when the weight average molecular weight of a polymer is less than 500, manufacture of a polymer may become difficult.

It is preferable that content of the polymer in a composition is 10-200 mass parts on the basis of 100 mass parts of thermoplastic resins. When content of a polymer is less than 10 mass parts, there exists a tendency for the plasticization effect to fall by a polymer. On the other hand, when content of a polymer exceeds 200 mass parts, the composition obtained will become too soft and it will become difficult to shape | mold a workpiece.

Furthermore, the viscosity of the polymer is preferably 100,000 cP or less, more preferably 50,000 cP or less, and particularly preferably 20,000 cP or less, as measured by a B-type viscometer at 25 ° C. The reason for this is that when the viscosity is high, a sufficient plasticizing effect may not be obtained. The lower limit of the viscosity is not particularly limited, but the viscosity of the polymer is generally 100 cP or more.

Moreover, it is preferable that the glass transition temperature (Tg) measured by the differential scanning calorimetry (DSC) is 0 degrees C or less, It is more preferable that it is -20 degrees C or less, It is especially preferable that it is -30 degrees C or less. When it exceeds 0 degreeC, a polymer may harden and it may not exhibit a plasticizing effect.

It is preferable that a polymer is obtained by superposing | polymerizing at 180-350 degreeC high temperature. By setting the polymerization temperature at 180 to 350 ° C, a polymer having a relatively low molecular weight and excellent plasticizing effect can be obtained without using a polymerization initiator and a chain transfer agent. The molded article of the composition to which the polymer is added is excellent in weather resistance, the strength is lowered, and the problem of coloring is improved. When the polymerization temperature is lower than 180 ° C, polymerization initiators and chain transfer agents are required for polymerization, coloring may occur in moldings, odor may occur, and weather resistance may decrease. When the polymerization temperature exceeds 350 ° C., decomposition reactions are liable to occur, and there is a risk of coloring occurring in the molded product.

Preferred polymerization methods for producing the polymer include a continuous polymerization method or a solution polymerization method. Particularly preferred is a continuous polymerization method using a stirred bed reactor. Since the molecular weight distribution is reduced by polymerization at a high temperature, a polymer having a balance between an excellent plasticizing effect and a molded article containing a polymer that is hard to be sticky is obtained. In addition, although a polymerization initiator does not need to be used even if it is used, when using, it is preferable to set it as the density | concentration of 1 mass% or less.

Some of the obtained polymers have a double bond at the terminal. The polymer which has a double bond at the terminal is preferable because it has especially excellent compatibility when used as a plasticizer, and as a result, there is little risk that it becomes sticky on the surface of the molded object with which the plasticizer was mix | blended. The reason for this is presumed that the terminal double bond possessed by the polymer is to react with other components in the molding.

Preferably the ratio of the polymer which has a double bond at the terminal is 20 mass% or more, More preferably, it is 40 mass% or more. The ratio is calculated from the average molecular weight determined by gel permeation chromatography (GPC) and the concentration of the double bond determined by its magnetic resonance spectrum (NMR). The average number of terminal double bonds (the total number of terminal double bonds divided by the number of molecules of the polymer) per one molecule of the polymer thus obtained is referred to as the terminal double bond index.

The said polymer has preferable plasticization efficiency of 30-150, More preferably, it is 40-100, More preferably, it is 40-90, Most preferably, it is 40-80. Here, plasticization efficiency means the quantity (mass part) of the polymer which gave the shore hardness (A or D) equivalent to the case where 50 mass parts of dioctyl phthalates (DOP) are added to plasticized resin. If the numerical value of the plasticization efficiency is too large, the compatibility between the polymer and the resin becomes poor, or the strength and elongation of the resulting molded product are reduced. It is not a problem that the numerical value of plasticization efficiency is small, but it is difficult to manufacture a polymer whose plasticization efficiency is smaller than 30 normally.

When the polymer is used for plasticizing the vinyl chloride resin, the weight average molecular weight of the polymer is preferably 500 to 4000, more preferably 500 to 2000, and even more preferably 500 to 1800 for the aforementioned reasons. The Q value (hereinafter, simply referred to as Q value) of the polymer by the water tolerance method is preferably 11.5 to 16, and more preferably 12 to 16. Preferably the ratio of the butyl acrylate unit with respect to the monomeric unit which comprises a polymer is 60 mass% or more. Such angular values produce the effect of delaying the gelation of the composition during molding of the composition, and also produce the effect of reducing the maximum value of this torque in the composition.

The calculation method of the Q value will be described in more detail below. 0.5 g of sample is taken in a Konica beaker and the sample is dissolved by the addition of 50 ml of acetone. The solution is added in small portions until white turbidity occurs. Using the amount (ml) of water added to the turbidity, the Q value is calculated by the following equation.

Q value = 50 (ml) × 9.77 / (volume of mixed solution of acetone and water (ml)) + W (ml) × 23.5 / (volume of mixed solution of acetone and water (ml))

Where W is the amount of water (ml) added to the turbidity. The numerical value [9.77] is the value of the solubility parameter of acetone (SP value), and the numerical value [23.5] is the SP value of water.

On the other hand, when the polymer is used for plasticizing the ABS resin or the acrylic resin plastisol, the Q value of the polymer is preferably 13.5 to 16.

When a polymer is used for plasticizing the sealing material, the polymer average molecular weight of the polymer is preferably 500 to 10,000. The sealing material using the polymer of the present invention can be suitably used in the construction field and civil engineering. Moreover, the polymer can be used as processing aids, extenders, fillers and the like of synthetic resins.

Next, examples of the thermoplastic resin included in the composition of the present invention will be described in more detail. Resin that can be used is polymethyl methacrylate resin (PMMA resin), vinyl chloride resin in the form of plastisol, acrylonitrile diene styrene resin (ABS resin), AXS resin, acrylic resin in the form of plastisol, Urethane resins, olefin resins, polystyrene resins, polycarbonate resins, crystalline polyester resins, amorphous polyester resins, and the like. Among them, polymethyl methacrylate resin, vinyl chloride resin, ABS resin and AXS resin are preferred because they are excellent in compatibility with the polymer and promote plasticization.

In the present specification, AXS resin is a resin in which butadiene, which is a rubber component of ABS resin, is substituted with a rubber component other than butadiene. In other words, AXS resin is resin which copolymerized styrene with rubber components other than acrylonitrile and butadiene. AXS resin is specifically ASA resin containing acrylic rubber as rubber component (named AAS resin), ACS resin containing chlorinated polyethylene as rubber component, AES resin containing ethylene propylene rubber as rubber component, ethylene- as rubber component Resins containing vinyl acetate copolymers, AOS resins containing olefins as rubber components, and the like. In the present specification, the rubber component of the AXS resin is a concept including a mixture such as a polymer of the rubber component as long as it is a component other than butadiene. Examples of crystalline polyester resins include polyethylene terephthalate (PET), and examples of amorphous polyester resins include polyesters obtained from terephthalic acid, ethylene glycol and cyclohexanedimethanol.

The thermoplastic resin composition of the present invention may contain a rubber component, a filler, an antioxidant, an ultraviolet absorber or other additives. As a rubber component, acrylic rubber, butadiene rubber, styrene-butadiene copolymer rubber, etc. are mentioned. Examples of the filler include calcium carbonate, talc (talc), cray (clay), magnesium hydroxide, glass fibers and the like. As an antioxidant, 3- (3,5-di-t- butyl- 4-hydroxyphenyl) propionate, phenolic antioxidants, such as bisphenol A, saritil antioxidants, such as 4-t- butylphenyl saritrilate And benzophenone-based antioxidants such as 2-oxy-4-methoxy benzophenone.

Examples of the ultraviolet absorber include an oxaric acid anide-based ultraviolet absorber such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole-based ultraviolet absorber, 2-ethoxy-2'ethyloxaric acid bisanilide, and bis Hindamine type ultraviolet absorbers, such as (2,2,6,6- tetramethyl-4- piperzyl) sebacate, etc. are mentioned. Other additives include pigments, aggregates, processing aids and blowing agents.

Hereinafter, the above embodiment will be described more specifically with reference to Examples and Comparative Examples. In each of the following examples,% means mass%.

(Production Example)

(Polymer 1)

A 500 ml capacity pressurized stirring agitation reactor equipped with an oil jacket was filled with ethyl 3-ethoxypropionate. The temperature was maintained at 245 ° C., and the pressure was maintained at a gauge pressure of 3.0 MPa (30 kg / cm ² ) by a pressure regulator.

Next, continuous supply of the monomer mixture was started from the raw material tank to the reactor at a constant feed rate (42 g / min, residence time: 12 minutes) while maintaining the pressure of the reactor constant. The monomer mixture is 70 parts by mass of ethyl acrylate (hereinafter referred to as EA), 30 parts by mass of methoxyethyl acrylate (hereinafter referred to as C1), 30 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK), and dibutyl butyl wave It consisted of 2 mass parts of oxides. Here, EA and C1 are the raw material monomers of the polymer, MEK is the solvent, and dibutyl butyl poxide is the polymerization initiator.

And the amount of reactants corresponding to the supply amount of the monomer mixture was continuously drawn out from the outlet. Immediately after the start of the supply, the reaction temperature was lowered and then the temperature was increased in the heat of polymerization, but the reaction temperature was maintained at 245 ° C by controlling the oil temperature of the jacket.

After the start of supply of the monomer mixture, the temperature was stabilized as the start of recovery of the reaction solution, and the reaction was continued for 154 minutes therefrom. About 6500 g of the monomer mixture was supplied, and the reaction solution was recovered. Volatile components such as unreacted monomers and solvents in the reaction liquid were removed under reduced pressure at 250 ° C. and 30 kPa · s by continuously introducing the recovered reaction liquid into the thin film evaporator. About 4000 g of liquid resin (polymer 1) was obtained. As a result of gas chromatography analysis, unreacted monomer was less than 0.5% in the liquid resin.

The number average molecular weight (hereinafter abbreviated as Mn) of the polymer 1 obtained by using polyhydrofuran as a solvent and obtained by gel permeation chromatography (hereinafter referred to as GPC) in terms of polystyrene is 1710, and the weight average molecular weight (hereinafter referred to as Mn). , Abbreviated as Mw) was 2100 and the polydispersity was 1.52. The Q value was 12.7 and the terminal double bond index was 0.70. The viscosity at 25 degrees C measured by the Brookfield viscometer was 3800 cP.

(Polymer 2-10)

Except having changed the composition of the used monomer as shown in Table 1, the same process as the manufacture case of the said polymer 1 was performed, and the polymers 2-10 were obtained, respectively. In Table 1, BA represents butyl acrylate and St represents styrene. In addition, [-] in Table 1 shows that it is unmeasured. Table 1 shows Mw, viscosity and composition for each of the obtained polymers.

Table 1

polymer Mw Viscosity Furtherance Production Example Polymer 1 2100 3800 EA / C1 = 70/30 Polymer 2 2160 1907 BA / C1 = 70/30 Polymer 3 1290 365 BA / C1 = 70/30 Polymer 4 1960 1234 BA / C1 = 55/45 Polymer 5 1300 370 BA / C1 = 55/45 Polymer 6 2200 900 BA / C1 = 55/45 Polymer 7 1740 - BA / C1 = 55/45 Polymer 8 1800 560 BA / C1 = 45/55 Polymer 9 2290 1581 BA / C1 = 30/70 Polymer 10 2040 - St / C1 = 10/90 Comparative Example Polymer 11 1230 2710 EA = 100 Polymer 12 2200 3400 EA / BA = 70/30 Polymer 13 2290 1907 EA / BA = 50/50 Polymer 14 2700 - BA / C1 = 90/10 Polymer 15 2500 - BA / C1 = 85/15

(Manufacture comparison example)

(Polymer 11)

It was set in a water bath, and 500 g of methyl ethyl ketone (hereinafter referred to as MEK) was added to a 3 L flask equipped with a stirrer as a solvent, and the temperature was adjusted to 80 ° C. And the monomer solution was continuously added to the flask over 4 hours at constant speed. The monomer solution consisted of EA 700g as a monomer, mercaftethanol 70g as a chain transfer agent, 200g MEK as a solvent, and 30g azobisisobutyronitrile as a polymerization initiator. During the reaction, the temperature was maintained at 80 ° C., and the supply of the monomer solution was terminated, followed by aging at 80 ° C. for 1 hour.

The obtained reaction liquid was introduced into a thin film evaporator, and volatile components, such as unreacted monomer, were removed under reduced pressure of 235 degreeC and 30 mmHg, and 980 g of liquid resin (polymer 11) was obtained. As a result of gas chromatography analysis, unreacted monomer was less than 0.5% in the liquid resin.

Mn of the polymer 11 which polystyrene reduced the molecular weight calculated | required by GPC using tetrahydrofuran as a solvent was 680, Mw was 1230, and polydispersity was 1.81. The viscosity at 25 degrees C measured by the Brookfield viscometer was 2710 cP.

(Polymer 12-15)

The polymer was used as described in Table 1, and the same procedure as in the case of the production of polymer 11 was carried out except that it was changed using ethyl mercaptate acetate as a chain transfer agent. Got. Table 1 shows Mw, the viscosity, and the composition of the obtained polymers 12-15.

In Table 1, BA represents butyl acrylate and St represents styrene.

(Production Example)

(Polymer 16-19)

Polymers 16 to 19 were prepared in a manner similar to that of polymer 11 at a polymerization temperature of 80 ° C. The monomer composition of the raw material, and Mw and viscosity of the produced polymers 16-19 are shown in Table 2.

Table 2

polymer Mw Viscosity Furtherance Production Example Polymer 16 1700 2600 EA / C1 = 70/30 Polymer17 2100 500 BA / C1 = 70/30 Polymer18 2000 850 BA / C1 = 55/45 Polymer19 2400 1500 BA / C1 = 30/70

(Examples 1 to 21: plasticization of vinyl chloride resin)

Polymers 1 to 7 were used as plasticizers in the amounts shown in Table 3. The polymers 1-7 were mix | blended with 100 mass parts of vinyl chloride resins with a thermal stabilizer. As the vinyl chloride resin, a resin (TS-1300 manufactured by Dong-A Synthetic Co., Ltd.) having a polymerization degree of 1300 was used. The mixture of 1.2 mass parts of calcium stearate (SC-100 by Sakai Chemical Co., Ltd.), and 0.3 mass part of zinc stearate (SZ-2000 by Sakai Chemical Co., Ltd.) was used for the thermal stabilizer.

A vinyl chloride resin, a heat stabilizer, and a plasticizer were mixed, and a sheet having a thickness of 1 mm was prepared by using a press molding machine on the mixture. Then, the tensile strength, 100% modulus and elongation (%) were measured and evaluated. The results are shown in Table 3.

Table 3

polymer Tensile Test Results Elongation (%) Added amount (PHR) Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Example 1 Polymer 1 50 21.0 14.2 377 Example 2 65 19.7 11.1 321 Example 3 80 15.1 7.8 292 Example 4 Polymer 2 50 23.5 17.8 269 Example 5 65 22.1 13.5 324 Example 6 80 18.4 7.8 365 Example 7 Polymer 3 50 24.8 14.9 324 Example 8 65 18.0 6.5 384 Example 9 80 17.7 6.3 392 Example 10 Polymer 4 50 25.2 17.8 286 Example 11 65 25.0 15.1 300 Example 12 80 19.5 8.8 357 Example 13 Polymer 5 50 24.0 12.7 343 Example 14 65 21.9 9.8 344 Example 15 80 20.0 9.4 322 Example 16 Polymer 6 50 24.2 15.6 298 Example 17 65 20.4 10.1 327 Example 18 80 16.3 7.1 331 Example 19 Polymer 7 50 23.2 15.9 278 Example 20 65 20.7 11.0 309 Example 21 80 17.1 7.3 342

As shown in Table 3, Examples 1 to 21 were also good in tensile strength, 100% modulus and elongation (%). 100% modulus is the tensile stress when 100% elongation is given. Except not adding Polymer 1, the tensile test of the vinyl chloride resin was carried out in the same manner as in Example 1, the elongation was 51%.

(Examples 22 to 31 and Comparative Examples 1 to 10: plasticization of ABS resin)

In Examples 22 to 31, an ABS resin (Techno-ABS170 manufactured by Technopolymer Co., Ltd.) and polymers (polymers 3 to 5 and 7, 10) of the addition amounts shown in Table 4 were mixed, and the blend was molded into a sheet having a thickness of 2 mm. In Comparative Example 1, the same sheet was formed using only ABS resin without adding a polymer. In Comparative Examples 2-10, when the polymer 12-15 as shown in Table 4 was added with respect to ABS resin, the sheet was produced similarly. In such a sheet, the surface hardness (Shore hardness) was measured at the same time as the tension test was performed. The results are shown in Table 4. The tensile test was carried out by producing a type 1 test piece in accordance with JIS K7113 (tensile test). In addition, the surface hardness was measured according to JIS K7215 (durometer D hardness).

Table 4

polymer Tensile Test Results Elongation (%) Shore hardness D Added amount (PHR) Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Example 22 Polymer 3 40 9.8 9.7 100 59 Example 23 50 8.0 7.6 119 52 Example 24 Polymer 4 50 8.7 8.2 114 52 Example 25 Polymer 5 50 6.4 5.9 118 45 Example 26 Polymer 7 50 6.2 4.4 263 47 Example 27 80 1.1 0.5 284 3 Example 28 Polymer 10 40 14.6 11.5 148 - Example 29 50 8.9 6.8 220 - Example 30 60 7.3 4.2 279 - Example 31 Polymer 5 100 0.1 0.1 556 17 Comparative Example 1 none 0 30.0 - 23 71 Comparative Example 2 Polymer 12 30 Not rated - - Comparative Example 3 50 Not rated - - Comparative Example 4 Polymer 13 30 Not rated - - Comparative Example 5 40 17.7 - 3 - Comparative Example 6 50 9.8 - 2 - Comparative Example 7 Polymer 14 30 Not rated - - Comparative Example 8 50 Not rated - - Comparative Example 9 Polymer 15 30 Not rated - - Comparative Example 10 50 Not rated - -

In Table 4, the molded articles of Examples 22 to 31 using the polymers 3 to 5 and 7, 10 had a particularly high elongation, a good 100% modulus, and could maintain the elongation strength and the shore hardness. When the addition amount of the polymer 7 was 80 parts by mass (Example 27), the performance was lowered. On the other hand, Comparative Examples 1 to 10 could not be evaluated because the desired performance was not obtained or the compatibility between the ABS resin and the polymer was poor.

(Examples 32 and 33 and Comparative Example 11: Plasticization of ABS Resin)

As shown in Table 5, in Examples 32 and 33, ABS resin (Phycolac EX101, manufactured by Ube-Scicon Co., Ltd.) and the polymer (Polymer 1 and Polymer 8) were mixed, and the mixture was formed into a sheet having a thickness of 2 mm. . On the other hand, Comparative Example 11 was a case in which Polymer 11 was added, and thus a sheet was produced in the same manner as in Examples 32 and 33. In such a sheet, a tensile test was performed. The results are shown in Table 5.

Table 5

polymer Tensile Test Results Elongation (%) Added amount (PHR) Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Example 32 Polymer 1 50 21.6 14.1 130 Example 33 Polymer 8 50 10.5 9.5 185 Comparative Example 11 Polymer 11 50 19.0 - One

As shown in Table 5, the molded articles using the polymers 1 and 8 in Examples 32 and 33 had particularly good elongation as compared with the molded articles of Comparative Example 11.

(Examples 34 to 41: Plasticization of Polymethylmethacrylate Resin)

80 parts by mass of the polymer 7 or 9 was mixed as a plasticizer in 100 parts by mass of the various polymethyl methacrylate resins shown in Table 6, and the blend was molded into a sheet having a thickness of 1 mm. In such sheets, the elongation strength, 100 modulus and elongation were measured and evaluated. The results are shown in Table 6.

Table 6

polymer PMMA resin The tensile strength 100% modulus Elongation Kinds amount Kinds amount (N / mm ² ) (N / mm ² ) (%) Example 34 Polymer 7 80 copies Derpet 560F 100 copies 4.1 5.8 160 Example 35 〃 〃 Derpet 60N 〃 4.1 3.5 189 Example 36 〃 〃 Derpet LP-1 〃 6.5 4.7 184 Example 37 Polymer 9 〃 Derpet 560F 〃 3.5 3.1 179 Example 38 〃 〃 Derpet 60N 〃 3.3 2.5 180 Example 39 〃 〃 Derpet LP-1 〃 5.6 4.4 194 Example 40 〃 〃 Acripet IP H70 〃 7.2 3.8 236 Example 41 〃 〃 AcripetMF001 〃 7.2 4.0 223

As shown in Table 6, Examples 34 to 41 all obtained values with good tensile strength, 100% modulus and elongation.

(Examples 42-47 and Comparative Examples 12-14: plasticization of polymethyl methacrylate resin)

Examples 42 to 47 kneaded 80 parts by mass of polymer 9 shown in Table 7 as a polymer and 100 parts by mass of polymethyl methacrylate resin, and the resulting mixture was molded into a sheet having a thickness of 1 mm. On the other hand, Comparative Examples 12-14 were the case where polymer 11 was added with 100 mass parts of polymethylmethacrylate resins, and the sheets were produced similarly to Examples 42-47. The appearance and the degree of fragility were measured in such sheets. The results are shown in Table 7.

Table 7

polymer PMMA resin Exterior Hard to break Kinds amount Kinds amount Example 42 Polymer 9 80 copies Derpet 560F 100 copies Transparency O Example 43 〃 〃 Derpet 60N 〃 〃 O Example 44 〃 〃 Derpet LP-1 〃 〃 △ Example 45 〃 〃 AcripetIR H30 〃 〃 △ Example 46 〃 〃 AcripetIR H70 〃 〃 O Example 47 〃 〃 AcripetIR G504 〃 〃 △ Comparative Example 12 Polymer 11 80 copies Derpet 560F 100 copies 〃 × Comparative Example 13 〃 〃 Derpet 60N 〃 〃 × Comparative Example 14 〃 〃 Derpet LP-1 〃 opacity ×

As shown in Table 7, the molded articles of Examples 42 to 47 were transparent in appearance and hard to break. On the other hand, the molded articles of Comparative Examples 12 to 14 were easily broken and the appearance was opaque. In [Difficult to break] in Table 7, 0 indicates that the molded product is hard to be broken,? Indicates that the molded product is more easily broken than the case of 0, but more difficult to break than x, and x indicates that the product is easily broken.

(Examples 48, 49 and Comparative Example 15: Plasticization of ASA Resin)

50 mass parts of polymer 1 or polymer 8 shown in Table 8 as a plasticizer was mixed with 100 mass parts of ASA resin which is a copolymerization resin of acrylonitrile, styrene, and acrylic acid ester, and the blend was shape | molded into the sheet of thickness 1mm. On the other hand, Comparative Example 15 was a case in which no polymer was added, and thus a sheet was produced in the same manner as in Examples 48 and 49. In such a sheet. Tensile strength, 100% modulus and elongation were measured and evaluated. The results are shown in Table 8.

Table 8

polymer Tensile Test Results Elongation (%) Added amount (PHR) Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Comparative Example 15 none 0 28.2 - 55 Example 48 Polymer 1 50 8.0 6.2 201 Example 49 Polymer 8 50 5.0 4.6 199

As shown in Table 8, all of Examples 48 and 49 obtained good values in tensile strength, 100% modulus and elongation. In contrast, Comparative Example 15, in which the polymer was not added, was particularly poor in elongation rate.

(Examples 50-61: Plasticization of Vinyl Chloride Resin)

The sheet was molded in the same manner as in Example 1 except that Polymers 16 to 19 were used instead of Polymer 1. Tensile strength, 100% modulus and elongation (%) were measured and evaluated. The results are shown in Table 9.

Table 9

Example No. polymer Tensile Test Results Kinds amount Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Elongation (%) Example-50 Example-51 Example-52 Polymer 16 506580 20.51917 15.512.18 350300280 Example-53 Example-54 Example-55 Polymer17 506580 2422.519 1714.58.5 300320380 Example-56 Example-57 Example-58 Polymer18 506580 252117 15107.5 320350370 Example-59 Example-60 Example-61 Polymer19 506580 211916 1587.5 300340370

(Examples 62 to 67: Plasticization of ABS Resin)

A sheet was prepared in the same manner as in Example 22 except that Polymers 17 and 18 were used instead of Polymer 3. In such a sheet, the surface hardness (Shore hardness) was measured at the same time as the tension test was performed. The results are shown in Table 10.

Table 10

Example No. polymer Tensile Test Results Kinds amount Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Elongation (%) Example-62 Example-63 Example-64 Polymer17 405060 108.58 1087 150140140 Example-65 Example-66 Example-67 Polymer18 405060 1386.5 1265 200220260

(Examples 68-73: Plasticization of Polymethylmethacrylate (PMMA) Resin)

The sheet was molded in the same manner as in Example 37 except that the polymer 19 was used instead of the polymer 9 and the kind of PMMA resin was changed as shown in Table 11. In Table 11, a terpet and an acripet are brand names of the polymethyl methacrylate resin made from Asahi Kasei Co., Ltd. and Mitsubishi Rayon Co., Ltd., respectively. In such sheets, tensile strength, 100% modulus and elongation were measured and evaluated. The results are shown in Table 11.

Table 11

Example No. polymer PMMA resin Tensile Test Results Kinds amount Kinds amount Tensile Strength (N / mm ² ) 100% Modulus (M / mm ² ) Elongation (%) Example-68 Polymer19 80 copies Derpet 560F 100 copies 4 4 200 Example-69 Polymer19 80 copies Derpet 60N 100 copies 3.5 3 210 Example-70 Polymer19 80 copies Derpet LP-1 100 copies 6 4 230 Example-71 Polymer19 80 copies AcripetIR H30 100 copies 7 4 160 Example-72 Polymer19 80 copies AcripetIR H70 100 copies 7.6 4.5 220 Example-73 Polymer19 80 copies AcripetIR G504 100 copies 5.5 4 175

The present invention can also be implemented by changing the above embodiment as follows.

For example, the polymer may be formed only of the monomer units represented by any of Formulas (1) to (4). In addition, the polymer may be a combination of two or more types of monomer units in the monomer units represented by the formulas (1) to (4), or may be monomers composed of a plurality of homogeneous monomer units having different m or R in the same formula. good.

In a specific embodiment, a plurality of polymers having different plasticizing effects may be prepared in advance, and the polymers may be appropriately mixed and used so as to meet the flexibility of the target molding.

According to the present invention, a thermoplastic resin composition having a high plasticizing effect and good flexibility is provided.

Claims (9)

A thermoplastic resin composition comprising a polymer comprising at least 20% by mass of monomer units represented by any one of Formulas (1) to (4) and 80% by mass or less of other monomer units, and a thermoplastic resin. CH ₂ = CHCOO (CH ₂ CH ₂ O) m -R. (One) CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) m R. (2) CH ₂ = CHCOO (CH ₂ C (CH ₃ ) HO) m R. (3) CH ₂ = C (CH ₃ ) COO (CH ₂ C (CH ₃ ) HO) m R. (4) (In formulas (1) to (4), m is 1, 2, or 3, and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, except that m is 1 and R is a hydrogen atom.) The method of claim 1, The thermoplastic resin composition, characterized in that the weight average molecular weight of the polymer is a low molecular weight of 500 ~ 10,000. The method of claim 1, A thermoplastic resin composition, based on 100 parts by mass of the thermoplastic resin, and having a polymer content of 10 to 200 parts by mass. The method according to any one of claims 1 to 3, The thermoplastic resin composition, characterized in that the polymethyl methacrylate resin. The method according to any one of claims 1 to 3, The thermoplastic resin composition, characterized in that the vinyl chloride resin. The method according to any one of claims 1 to 3, The thermoplastic resin composition, characterized in that the acrylonitrile-butadiene-styrene copolymer. The method according to any one of claims 1 to 3, The thermoplastic resin is a thermoplastic resin composition of acrylonitrile, rubber components other than butadiene, and styrene copolymer (AXS resin). The method according to any one of claims 1 to 3, A thermoplastic resin composition, characterized in that it has an elongation of 30% or more greater than the elongation of the thermoplastic resin. Processed article manufactured using the thermoplastic resin composition according to any one of claims 1 to 3.